Process of killing nematodes and fungi with halo vinyl and haloethyl thio cyclic imides



United States Patent PRQCESS 0F KILLING NEMATODES AND FUNGI WITH HALOVINYL AND HALOETHYL THIO CYCLIC IMIDES Paul C. Aichenegg, PrairieVillage, Kans., Carl D. Emerson, Kansas City, Mo., and Noel B. Jarnevic,Kansas City, Karts, assignors to Chemagro Corporation, New York, N.Y., acorporation of New York No Drawing. Original application May 29, 1962,Ser. No. 198,431. Divided and this application Mar. 29, 1963, Ser. No.269,203

14 Claims. (Cl. 167-33) This application is a division of applicationSerial No. 198,431, filed May 29, 1962.

This invention relates to novel sulfenylated cyclic imides and their useas pesticides.

It is an object of the present invention to prepare novel halovinylthiocyclic imides.

Another object is to prepare novel haloethylthio cyclic imides.

An additional object is to prepare novel halovinylthio cyclicsulfenimides and haloethylthio cyclic sulfenimides.

A further object is to develop a novel method of killing nematodes.

Yet another object is to develop a novel method of killing fungi.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by Way of illustration only,since various changes and modifications Within the spirit and scope ofthe invention will become apparent to those skilled in the art from thisdetailed description.

It has been found that these objects can be attained by preparingcompounds having one of the formulae where X is selected from the groupconsisting of and Y is selected from the group consisting of u (1 7 -oan0 o except that when X is --C H Y is not two of Z Z and Z; are halogenof atomic weight 35 to 80, i.e., chlorine or bromine, and the othermember of Z Z and Z is hydrogen, 3 to 4 members of Z Z Z Z and Z arehalogen of atomic weight 35 to 80 and the remaining members of Z Z Z Zand Z are hydrogen and R is lower alkyl, chloro, bromo or nitro.

3,154,453 Patented Oct. 27, 1964 It has not been possible to prepare acompound where X is -C H and Y is and this is the reason suchcombination is excluded. It has been found that more effectivenematocides, fungicides and bactericides can be obtained when only twoof Z Z and Z, are halogen rather than when all three of Z Z and Z, arehalogen.

Illustrative of compounds according to the present invention areN-(1,2-dichlorovinylthio) phthalimide,

N-(2,2-dichlorovinylthio) phthalimide,

N-(1,2,2-trichloroethylthio) phthalimide,

N- (2,2,2-trichloroetl1ylthio) phthalimide,

N-(l,2-dibromovinylthio) phthalimide,

N-(2,2-dibromovinylthio) phthalimide,

N-( l-chloro-Z-bromovinylthio) phthalimide,

N-(1,2,2-tribromoethylthio) phthalimide,

N-(1,2,2,2-tetrachloroethylthio) phthalimide,

N-(l,2-dichloro-2-bromoethylthio) phthalimide,

N- 1 ,Z-dichlorovinylthio -3 -methylphthalimide,

N- (2,2-dichlorovinylthio -4-butylphthalimide,

N-( 1,2,2-trichloroethylthio -3 -ethylphthalimide,

N-(2,2,2-trichloroethylthio) phthalimide,

N-( 1,2-dichlorovinylthio -3 '-chlorophthalimide,

N- (2,2-dichlorovinylthio -3'-bromophthalimide,

N-( 1,2,2-trichloroethylthio -3-chlorophthalimide,

N- 2,2,2-trichloroethylthio -4'-chlorophthalimide,

N-( 1,2-dichlorovinylthio -3'-nitrophthalimide,

N-( 1,2-dichlorovinyltl1io) -cis-A -tetrahydrophthalimide,

N- (2,2-dichlorovinylthio -cis-A -tetrahydrophthalimide,

N (1,2,2 trichloroethylthio)-cis-A -tetrahydrophthalimide,

N (2,2,2 trichloroethylthio)-cis-A -tetrahydrophthalimide,

N (l,2,2,2-tetrachloroethylthio)-cis-A -tetrahydrophthalimide,

N (1,2 dibromovinylthio) cis-A -tetrahydrophthalimide,

N (1,2-dich1orovinylthio)-o-benzoic sulfimideN-(2,2-dichlorovinylthio)-o-benzoic sulfimide,

N- 1 ,2,'2-trichloroethylthio) -o-benzoic sulfimide,

N-(2,2,2-trichloroethylthio)-o-benzoic sulfimide,

N-(1,2,2,2-tetrach1oroethylthio)-o-benzoic sulfimide,

N- 1,2-dichlorovinylthio) -cis-M-tetrahydro-o-benzoic sulfimide,

N-(2,2-dichlorovinylthio)-cis-A -tetrahydro-o-benzoic sulfimide,

N (l,2,2-trichloroethylthio)-cis-A -tetrahydro-o-benzoic sulfimide N-1,2-dichlorovinylthio) succinimide, N-(2,2-dichlorovinylthio)succinimide, N-(1,2,2-trichloroethylthio) succinimide,

3 N-(2,2,2-trichloroethylthio) succinimide,N-(1-bromo-2,2-dichloroethylthio) succinimide, N- 1,2-dichlorovinylthio)-2-propionic sulfimide N-(2,2-dichlorovinylthio)-2-propionic sulfimide,N- 1,2,2-trichloroethylthio -2-propionic sulfimide,N-(2,2,2-trichloroethylthio)-2-propionic sulfimide,N-(1,2,2,2-tetrachloroethylthio) succinimide, N-(1,2-dichlorovinylthio)glutarimide, N-(2,2-dichlorovinylthio) glutarimide,N-(1,2,2-trichloroethylthio) glutarimide, N-(2,2,2-trichloroethylthio)glutarimide, N-(1,2-dichlorovinylthio) maleimide,N-(2,2-dichlorovinylthio) maleimide, N-(1,2,2-trichloroethylthio)maleimide, N-(2,2,2-trichloroethylthio) maleimide,N-(1,2,2,2-tetrachloroethylthio) maleimide, N-( 1,2-dichlorovinylthio-2-acrylic sulfimide, N-(2,2-dichlorovinylthio)-2-acrylic sulfimide, N-1,2,2-trichloroethylthio) maleimide, N-(2,2,2-trichloroethylthio)maleimide, N-(2,2-dibromovinylthio)-o-benzoic sulfimide,N-(1,2,2-trichloroethylthio) hexahydro-o-benzoic imide,N-(1,2-dibromovinylthio) succinimide, N-(1,2-dichlorovinylthio)hexahydro-o-benzoic sulfimide, N-(1,2,2-trichloroethylthio) hexahydro obenzoic sulfimide, N-(2,2-dibromovinylthio) maleimide,N-(1,2-dichlorovinylthio) hexahydrophthalimide,N-(2,2-dichlorovinylthio) hexahydrophthalimide, N-(1,2,2-tribromoethylthio)-2-propionic sulfimide, N-1,2,2-trichloroethylthio) hexahydrophthalimide,N-(2,2,2-trichloroethylthio) hexahydrophthalimide.

sulf- The compounds of the present invention are good nematocides andfungicides and in some instances are good bactericides.

The compounds of the present invention are prepared by reacting theappropriate alkali salt of the imide with the appropriate sulfenylchloride to split out alkali metal chloride as the by-product. Thealkali salt of the imide can be prepared by reacting an alkali metalalkoxide, e.g., sodium ethoxide, potassium ethoxide, sodium methoxide,potassium butoxide. Thus tetrahydrophthalimide (or succinimide) can bemixed with a slight excess of sodium ethoxide solution in absoluteethanol, the mixture filtered and the obtained crystalline imide saltdried over phosphorous pentoxide for 48 hours. Some of the alkali metalsalts of the imides, e.g., potassium phthalimide and sodium o-benzoicsulfimide are commercially available.

Examples of suitable starting imide salts are potassium phthalimide,sodium phthalimide, potasisum-3-methylphthalimide,sodium-4-butylphthalimide, potassium-3- ethylphthalimide,sodium-3-chlorophthalimide, potassium 3-bromophthalimide,potassium-4-chlorophthalimide, sodium-4-nitrophthalirnide,potassium-cis-M-tetrahydrophthalimide, sodium-o-benzoic sulfimide,potassium-cis-A -tetrahydro-o-benzoic sulfimide, potassium succinimide,sodium 2-propionic sulfimide, potassium glutarimide, sodium maleimide,potassium-Z-acrylc sulfimide, sodium hexahydrophthalimide and potassiumhexahydroo-benzoic sulfimide.

As the starting sulfenyl chlorides there can be used 1,2-dichlorovinylsulfenyl chloride, 2,2-dichlorovinyl sulfenyl chloride, 1,2-dibromovinylsulfenyl chloride, 2,2- dibromovinyl sulfenyl chloride,1-chloro-2-bromovinyl sulfenyl chloride, 1,2,2-trichloroethyl sulfenylchloride,

2,2,2-trichloroethyl sulfenyl chloride, 1,2,2,2-tetrachloroethylsulfenyl chloride, 2,2,2-tribromoethyl sulfenyl chloride,1,2,2-tribromoethyl sulfenyl chloride, and 1,2-dichloro-2-bromoethylsulfenyl chloride.

The reaction between the alkali salt of the imide and the sulfenylchloride is preferably carried out in suspension in an inert solvent ator below room temperature. Thus 1 part of alkali imide salt is suspendedin 4 to 8 parts by weight of a solvent such as chloroform or carbontetrachloride and reacted with stirring and cooling With slightly lessthan an equimolar amount of the dichlorovinyl or trichloroethyl sulfenylchloride at 5- 10 C. by dropwise addition of the latter at a rate toinsure a smooth reaction. After stirring of the reaction mixture for anhour at room temperature, filtering (or alternatively washing theobtained suspension with water to remove unreacted alkali imide as wellas alkali chloride) drying of the organic solution over anhydrousmagnesium sulfate and stripping the obtained crude product isrecrystallized.

Alternatively the irnides of the present invention can be prepared byreacting a free imide, e.g., succinirnide, with the sulfenyl chloride inthe presence of a tertiary amine, e.g., trialkyl amines such astrimethyl amine, triethyl amine and tributyl amine and heterocyclicamines such as pyridine. Thus there can be used equimolar amounts of thefree imide and pyridine in 4 to 8 parts of chloroform or carbontetrachloride per part of free imide and the calculated amount ofsulfenyl chloride added. The unreacted pyridine is removed by washingwith dilute mineral acid followed by washing with water and sodiumbicarbonate solution in order to completely remove unreacted imide andpyridine hydrochloride. The product is dried and stripped of the organicsolvent and purified by conventional procedures.

The dichlorovinyl sulfenimides of the present invention can also beformed by dehydrochlorination of the corresponding trichlorethylcompounds, e.g., in the presence of a tertiary amine such as triethylamine.

Unless otherwise indicated all parts and percentages are by weight.

EXAMPLE 1 N-(1,2-dichl0r0vinylthio) phthalimide.11.4 grams (0.061 mole)of dry potassium pthalimide (0.2% water) suspended in about 6 parts ofchloroform per pant of potassium phthalimide were reacted in the mannerdescribed at 5-10 C. with about 10 grams (0.060 mole) of1,2-dichlorovinyl sulfenyl chloride which was added dropwise. Theresulting mixture was filtered and 1 volume of petroleum ether was addedto 1 volume of the chloroform solution. The precipitate formed containedthe desired N-(LZ-dichlorovinylthio) phthalimide and a small amount ofunreacted phthalimide starting material. Stripping of thechloroform-petroleum ether solution gave 5 grams (30% yield) of thedesired product as a white solid, M.P. 137139 C., Cl 25.0% (theory25.8%); N 5.7% (theory 5.1%); S 11.7% (theory 11.7% Recrystallizationfrom ethyl alcohol to remove the small amount of impurity present gavethe desired N-(1,2-dichloroviuylthio) phthalimide in pure form, M.P. 153154" C., 01 25.2%; S 12.0%; N 4.9%.

The low yield in this example was due to (1) the failure to work up thepotassium chloride which was first filtered off and contained aconsiderable amount of the desired product and (2) the failure toinclude the precipitate formed upon the additon of petroleum ether tothe filtrate. As indicated substantially all of the latter material wasthe desired N-(1,2-dichlorovinylthio) phthalimide.

EXAMPLE 2 N-(1,2-dichl0rovinylthio) cis A tetrahydrophthalimide.10.6grams (0.061 mole) of dry sodium tetrahydrophthalirnide (0.1% water)were suspended in about 6 parts of carbon tetrachloride per part ofsodium tetra- 5 hydrophthalimide and reacted at 5-10 C. in the mannerdescribed above with 10 grams (0.060 mole) of 1,2-dichlorovinyl sulfenylchloride. Filtration of the reaction mixture to remove sodium chloride,and stripping of solvent from the filtrate gave 15.5 grams (91% yield)of crude N-( 1,2-dichlorovinylthio) -cis-M-tetnahydrophthalimide as athick, faintly yellow oil which solidified on prolonged st anding.Recrystallization from ethanol gave white needles of the desiredproduct, M.P. 101-102 C., CI 27.8% (theory 25.5%); S 12.1% (theory11.5%); N 4.6% (theory 5.0%).

EXAMPLE 3 N-(1,Z-dichlorovinylthio) benzoic sulfimide.12.6 grams (0.078mole) of sodium o-benzoic sulfimide (containing 5.6% water) weresuspended in about 6 parts of carbon tetrachloride per part of sodiumo-benzoic sulfimide and reacted in the manner described above at 10 C.with 10 grams (0.060 mole) of 1,2-dichlorovinyl sulfenyl chloride. Themixture obtained was washed with water and filtered. There was obtainedgrams of insoluble material which was taken up into benzene, dried overmagnesium sulfate and reobtained after stripping oil the solvent ascrude N-( l,Z-dichlorovinylthio)-o-benzoic sulfimide in .a yield of 15grams (80% yield) as a faintly yellow solid, M.P. 99100 C. Washing twicewith ethyl alcohol gave the pure product as a white solid, M.P. 123-124C., Cl 22.6% (theory 22.9%); S 21.0% (theory 20.6%); N 4.4% (theory4.5%).

EXAMPLE 4 N-(1,2-dichl0r0vinylthio) succinimide. 10 grams (0.060 mole)of 1,2-dichlorovinyl sulfenyl chloride and 4.85 grams (0.060 mole) ofpyridine were added simultaneously by means of two separate droppingfunnels to a well stirred suspension of 12.2 grams (0.12 mole, i.e., 1mole excess) of succinimide at -30 C., during a period of 20 minutes.The rate of addition of the sulfenyl chloride was adjusted so as toguarantee a slight excess of the latter over the simultaneously addedpyridine in the reaction mixture. Stirring for an additional 1.5 hours,shaking with an equal volume of water and filtration of the totalmixture gave 7 grams yield) of crude N-(1,2-dichlorovinylthio)succinimide which was further purified by dissolving in chloroform,washing the solution twice with water, drying the organic layer overanhydrous magnesium sulfate and stripping off the solvent. The desiredproduct was obtained as an off white solid in an amount of 6.5 grams(46% yield) with a M.P. of 155-156 C. This product was further purifiedby taking it up in chloroform and precipitating it with petroleum etherto give white crystals, M.P. 159-160 C., Cl 31.8% (theory 31.4%); S14.3% (theory 14.2%).

EXAMPLE 5 N (2,2 dichlorovinylthio) phthalimide-42.0 grams (0.065 mole)of dry potassium phthalimide were suspended in about 6 parts of carbontetrachloride per part of potassium phthalimide and reacted in themanner described above at 5-10 C., with 10 grams: (0.060 mole) of2,2-dich1orovinyl sulfenyl chloride. The resulting suspension was washedwith water to remove potassium chloride and excess potassiumphthalimide. The organic layer was dried over anhydrous magnesiumsulfate and stripped of solvent to give 140 grams (84% yield) ofN-(2,2-dichlorovinylthio) phthalimide as a white crystalline solid, M.P.147-148 0., Cl 27.6% (theory 25.8%); S 11.4% (theory 11.7%); N 4.8%(theory 5.1% The product was further purified by recrystallization fromethyl alcohol, carbon tetrachloride and acetone. The recrystallizedproduct from acetone was the best and had a M.P. of 152-153" C., Cl26,2%; N 4.9%.

EXAMPLE 6 N (2,2 dichlorovinylthio) cz's A tetrahydro- 6phthalimide.-11.1 grams (0.064 mole) of dry sodium tetrahydrophthalimidesuspended in 6 parts of chloroform per part of sodiumtetrahydrophthalimide were reacted with 10 grams (0.060 mole) of2,2-dichlorovinyl sulfenyl chloride at 5-10 C., in the manner describedabove. The insolubles were removed by filtration and the solventstripped off to give 18 grams (100% yield) of N-(2,2-dichlorovinylthio)-cis-A -tetrahydrophthalimide as a faintly yellowsyrup which solidified on prolonged standing. The product wasrecrystallized from ethyl alcohol to give white needles, M.P. 96-97 C.,Cl 27.8% (theory 25.5%); S 11.7% (theory 11.5%); N 5.3% (theory 5.1%

EXAMPLE 7 N-(2,2 dichlorovinylthio)-o-benz0ic sulfimide.-10.2S grams(0.05 mole) of sodium o-benzoic sulfimide were suspended in 6 parts ofchloroform per part of sodium o-benzoic sulfimide and reacted in themanner described above at 510 C. with 8.15 grams (0.05 mole) of 2,2-dichlorovinyl sulfenyl chloride to give a suspension of sodium chloridein a chloroform solution of N-(2,2- dichlorovinylthio)-o-benzoicsulfimide. This mixture was washed with water, dried and the solventstripped off. After washing the residue with petroleum ether there wereobtained 15 grams (97% yield) of the described compound as a whitecrystalline solid, M.P. 122123 (3., Cl 23.0% (theory 23.2%); S 20.7%(theory 20.9%).

EXAMPLE 8 N-(2,2-dichl0r0vinylthi0) succinimide. 7.9 grams (0.065 mole)of dry sodium succinimide were suspended in 6 parts of chloroform perpart of sodium succinimide and reacted under the conditions set forthabove at 5-10 C. with 10 grams (0.060 mole) of 2,2-dichlorovinylsulfenyl chloride to give 14 grams (100% yield) of N-2,2-dichlorovinylthio) succinimide after removal of the sodium chloride byfiltration followed by stripping off of the organic solvent. The productwas a white crystalline solid which could be recrystallized from ethylalcohol, M.P. 158-159 C., Cl 31.6% (theory 31.4%); S 14.2% (theory14.2%); N 6.5% (theory 6.2%

EXAMPLE 9 N-(1,2,2-lrichl0r0ethylthio) phthalimide.l3.9 grams (0.075mole, a /2 mole excess) of potassium phthalimide in 6 parts ofchloroform per part of potassium phthalimide were treated with 10.0grams (0.05 mole) of 1,2,2- trichloroethyl sulfenyl chloride at 5-10 C.in the manner described above. A suspension resulted. This suspensionwas mixed with water, the water layer removed and all insolublesfiltered ofi. The organic layer was dried and stripped of solvent togive 12.0 grams (77% yield) of N-(1,2,2-trichloroethylthio) phthalimideas an almost white crystalline solid which could be recrystallized fromethyl alcohol, M.P. 111-112 C., Cl 34.2% (theory 34.2%); S 10.5% (theory10.3%); N 5.1% (theory 4.5%).

The reported yield can be increased by recovering the desired productwhich was removed by the initial filtra tion.

EXAMPLE 10 N-(l,2,2 trichloroethylthio) cz's Atetrahydrophthalimide-13.0 grams (0.75 mole, a /2 mole excess) of sodiumtetrahydrophthalimide suspended in 6 parts of chloroform per part ofsodium tetrahydrophthalimide were reacted in the manner described abovewith 10.0 grams (0.05 mole) of 1,2,2-trichloroethyl sulfenyl chloride at5-10 C. After washing with water, drying over magnesium sulfate andstripping off the chloroform solution there was obtained 15.0 gramsyield) of the N (1,2,Z-trichloroethylthio) -cis-A -tetrahydrophthalimideas a white crystalline solid, which was recrystallized from ethylalcohol, M.P. 91-92 C., Cl 34.1% (theory 33.8%); S 10.8% (theory 10.2%).

7 EXAMPLE 11 N-(1,2,2-trichlr0ethylthi0)-0-benzoic sulfimide.--20.5grams (0.1 mole) of sodium o-benzoic sulfimide suspended in 6 parts ofchloroform per part of sodium o-benzoic sulfimide were treated with 20.0grams (0.1 mole) of 1,2,2-trichloroethyl sulfenyl chloride at 10 C., andworked up in the manner previously described to give 31 grams (89.5%) ofN-(1,2,2-trichloroethylthio)-o-benzoic sulfimide as a white crystallinesolid, M.P. l08109 C. This product was recrystallized from carbontetrachloride to a M.P. 109110 C., Cl 30.1% (theory 30.8%); S 17.9%(theory 18.5%); N 4.3% (theory 4.1%).

EXAMPLE 12 N-(2,2,2-trichl0roethylthi0) phthalimide.18.5 grams (0.1mole, a 1 mole excess) of potassium phthalimide were suspended in 6parts of chloroform per part of potassium phthalimide and reacted in themanner described above with 10.0 grams (0.05 mole) of2,2,2-trichloroethyl sulfenyl chloride at 510 C. After removing theexcess unreacted imide salt and potassium chloride by Washing withwater, drying and stripping ofi. the chloroform there was obtained 13.5grams (87% yield) of N-(2,2,2-trichloroethylthio) phthalimide as a whitecrystalline residue, M.P. 169170 C. The product could be recrystallizedfrom ethyl alcohol, carbon tetrachloridechloroform (1:1 by volume) orpreferably from acetone with a M.P. of 183184 C., Cl 34.0% (theory34.2%);

S 9.7% (theory 10.3%); N 4.04% (theory 4.45%).

EXAMPLE 13 N-(2,2,2-trichl0r0ethylthio) cis-M-tetrahydrophthalimide.-9.1grams (0.053 mole) sodium tetrahydrophthalimide were suspended in 6parts of carbon tetrachloride per part of sodium tetrahydrophthalimideand reacted in the manner set forth above with 10.0 grams (0.05 mole) of2,2,2-trichloroethyl sulfenyl chloride at 510 C. The resulting mixturewas shaken with an equal volume of water and all insoluble materialcollected on the filter. The insolubles were taken up in benzene, washedwith water, dried over magnesium sulfate and the solvent evap orated togive 11.0 grams (70% yield) of N-(2,2,2-trichloroethylthio)-cis-A-tetrahydrophthalirnide as a white crystalline residue. After washingwith a light petroleum ether fraction and vacuum drying the product hada M.P. of 142143 C. Recrystallization can be accomplished from muchethyl alcohol or little acetone or chloroformcarbon tetrachloride (1:3by volume) to give a M.P. of 143144 C., Cl 33.3% (theory 33.8%); S 10.5%(theory 10.2%); N 4.31% (theory 4.45%).

EXAMPLE 14 N-(2,2,2-trichlor0ethylthio)-0-benzoic sulfimide.20.5 grams(0.1 mole) of sodium o-benzoic sulfimide were suspended in 6 parts ofchloroform per part of sodium o-benzoic sulfimide and reacted in themanner set forth above with grams (0.05 mole) of 2,2,2-trichloroethylsulfenyl chloride at 510 C. Washing with water to remove excessunreacted imide salt, drying and stripping off the chloroform yielded16.5 grams (95% yield) of N-(2,2,2-trichloroethylthio)-o-benzoicsulfimide as a white crystalline solid, M.P. 112113 C. The latter couldbe recrystallized from ethyl alcohol, acetone or carbon tetrachloride,M.P. 1l3114 C., Cl 31.1% (theory 30.5%); S 18.5% (theory 18.5%); N 3.7%(theory 4.0%).

EXAMPLE 15 N-(2,2,2-trichloroethylthio) succinimide.4.95 grams (0.05mole) of succinimide and 3.95 grams (0.05 mole) of pyridine in 50 ml ofchloroform were treated with 10.0 grams (0.05 mole) of2,2,2-trichloroethyl sulfenyl chloride at 30 C., and then warmed at 50C. for 0.5 hour to give a clear solution. This was washed with waterthree times, dried and stripped of solvents to give 5.0

8 grams (38% yield) of N-(2,2,2-trichloroethylthio) succinimide as anoff white solid, M.P. 101-103 C., CI 41.6% (theory 40.5%); S 12.7%(theory 12.2%); N 5.3% (theory 5.3%).

EXAMPLE 16 N-(2,2,Z-trichloroethylthio) succinimide.6.7 grams (0.055mole) of sodium succinimide were suspended in 6 parts of chloroform perpart of sodium succinimide and reacted with 10 grams (0.05 mole) of2,2,2-trichloroethyl sulfenyl chloride at 510 C. in the manner describedabove. After filtration and evaporation of the clear filtrate 13.0 grams(99.5% yield) of crude N-(2,2,2- trichloroethylthio) succinimide, M.P.104-105 C. was obtained. Two recrystallizations from carbontetrachloride gave the purified product, M.P. 108109 C., Cl 40.8%; S13.0%; N 5.1%.

EXAMPLE 17 N-(2,2-dichl0r0vinylthio) succinimide.5.0 grams (0.019 mole)of N-(2,2,2-trichloroethylthio) succinimide prepared in Example 16 weredissolved in 25 ml of chloroform and dehydrochlorinated with stirring bydropwise addition at room temperature of 2.0 grams (0.02 mole, a slightexcess) of triethyl amine. The reaction was exothermic and thetemperature of the mixture was kept between 35-40 C. by occasionalcooling with a cold water bath. The product was stirred for 1.5 hours atroom temperature (2528 C.), 50 ml. of chloroform added to dissolve theprecipitate formed, the clear chloroform solution washed successivelywith water, dilute hydrochloric acid and water, dried over anhydrousmagnesium sulfate and the organic layer stripped of solvent to give 4.0grams (93% yield) of crude N-(2,2-dichlorovinylthio) succinimide as alight-yellowish crystalline solid, M.P. 135-137 C. This wasrecrystallized from ethyl alcohol to give white shiny plates, M.P.159-160 C. which was identical with the product of Example 8, Cl 31.8%,S 15.7%, N 5.9%.

Chloroform proved to be a better solvent for the process than carbontetrachloride since the desired products were much more soluble in thechloroform.

As previously indicated the compounds of the present invention areuseful as nematocides and fungicides and in some cases as bactericides.The compounds of the present invention can be used alone as nematocides,fungicides and bactericides but it has been found desirable to applythem to the pest, e.g., to the soil habitat of nematodes, together withinert solids to form dusts or, more preferably, suspended in a suitableliquid diluent, preferably water. They can be applied at widely varyingrates, e.g., 0.1-30 lbs/acre.

There can also be added surface active agents or wetting agents andinert solids in such liquid formulations. Desirably, 0.051% by weight ofsurface active or wetting agent is employed. The active ingredient canbe from 0.01 to by weight of the entire composition in such case.

In place of water there can be employed organic solvents as carriers,e.g., hydrocarbons such as benzene, toluene, xylene, kerosene, dieseloil, fuel oil, and petroleum naphtha, ketones such as acetone, methylethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbontetrachloride, chloroform, trichloroethylene and perchloroethylene,esters such as ethyl acetate, amyl acetate and butyl acetate, ethers,e.g., ethylene glycol monomethyl ether and diethylene glycol monomethylether, alcohols, e.g., ethanol, methanol, isopropanol, amyl alcohol,ethylene glycol, propylene glycol, butyl carbitol acetate and glycerine.Mixtures of water and organic solvents, either an solutions oremulsions, can be employed.

The novel pesticides can also be applied as aerosols, e.g., bydispersing them in air by means of a compressed 9 gas such asdichlorodifluoromethane or trichlorofluoromethane and other Freons, forexample.

The pesticides of the present invention can also be applied withnema'tocidal, fungicidal and bactericidal adjuvants or carriers such astalc, pyrophyllite, synthetic fine silica, attapulgus clay, kieselguhr,chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fullersearth, cottonseed hulls, wheat flour, soybean flour, pumice, tripoli,wood flour, walnut shell flour, redwood flour and lignin.

It is frequently desirable to incorporate a surface active agent in thepesticidal compositions of the present invention. Such surface active orwetting agents are advantageously employed in both the solid and liquidcompositions. The surface active agent can be anionic, cationic ornonionic in character.

Typical classes of surface active agents include alkyl sulfonate salts,alkylaryl sulfonate salts, alkyl sulfate salts, alkylamide sulfonatesalts, alkylaryl polyether alcohols, fatty acid esters of polyhydricalcohols and the alkylene oxide addition products of such esters, andaddition products of long chain mercaptans and alkylene oxides. Typicalexamples of such surface active agents include the sodium alkylbenzenesulfonates having to 18 carbon atoms in the alkyl group, alkylphenolethylene oxide condensation products, e.g., p-isooctylphenol condensedwith 10 ethylene oxide units, soaps, e.g., sodium stearate and potassiumoleate, sodium salt of propylnaphthalene sulfonic acid, (di2-ethylhexyl)ester of sodium sulfosuccinic acid, sodium lauryl sulfate, sodium saltof the sulfonated monoglyceride of cocoanut fatty acids, sorbitansesquioleate, lauryl trimethyl ammonium chloride, octadecyl trimethylammonium chloride, octadecyl trimethyl ammonium chloride, polyethyleneglycol lauryl ether, polyethylene esters of fatty acids and rosin acids,e.g., Ethofat 7 and 13, sodium N-methyl-N-oleyltaurate, Turkey red oil,sodium dibutylnaphthalene sulfonate, sodium lignin sulfonate (MarasperseN), polyethylene glycol stearate, sodium dodecylbenzene sulfonate,tertiary dodecyl polyethylene glycol thioether (Nonionic 218), longchain ethylene oxide-propylene oxide condensation products, e.g.,Fluronic 61 (molecular weight 1000), sorbitan sesquioleate, polyethyleneglycol ester of tall oil acids, sodium octyl phenoxyethoxyethyl sulfate,tris(polyoxye'thylene) sorbitan monostearate (Tween 60), sodium dihexylsulfosuccinate.

The solid and liquid formulations can be prepared by any of theconventional procedures. Thus, the active ingredient can be mixed withthe solid carrier in finely divided form in amounts small enough topreserve the free-flowing property of the final dust composition.

In the following examples or tables illustrating nematocidal andfungicidal activity the sulfenylated cyclic imides were formulated aswettable powders consisting of 50% of the sulfenylated cyclic imide, 46%ultra fine silica (Hi-Sil), 2% sodium lignin sulfonate and 2% PluronicL-6l (polyethylene oxide-polypropylene oxide adduct,

10 molecular weight about 1000). This wettable powder is hereinafterdesignated as Formulation A.

Formulation A was diluted with water to such an extent to give the finalconcentrations of the sulfenylated cyclic imide indicated in Table 1.

The sapropyhytic nematode tests recorded in Table l were carried out inwater as the medium with Panagrellus and Rhabditis spp. at roomtemperature. The results were recorded as percent kill after a 2-dayincubation period. The blank mortality was 010% kill.

In all of the tables the following abbreviations are used A forphthalimido A for A -tetrahydrophthalirnido A for o-benzoic-sulfimido Afor succinimido Table 1 Percent Kill of Nematodes at Rates p.p.m.Compound AiSCC1= CHCl 100 100 90 90 50 AzSCCl=GHCl 100 100 100 100 80AaSCCl=CHCl -l 100 100 50 0 0 AiSCCl= CHCl 100 109 90 80 50 A1SCH=CC12 a100 100 100 30 A2SCH=CCla 60 60 30 0 0 AsSCI-I: C012 100 100 100 100 100A4SCH=OCl2 100 100 100 50 AiSCHClCHCl2 100 100 80 80 80 A2SCHClCHClg 9060 30 0 AQSQHCICHCIL 100 80 40 20 A18 oHaC Cls 30 0 0 0 0 AzSCHzCCla. 8040 0 0 0 AaSCHzC Clsl 100 103 80 60 60 AlSOHzC C13. 100 100 80 80 50Compound A SCH:CCl was so outstanding that it was tested at lowerdosages with the following results Percent kill at 6 p.p.m. 3 p.p.m. 1p.p.m.

AsSCH=CClz 50 2O 0 In commercial practice the compositions containingthe nematocides of the present invention are applied to the soilinfected with nematodes.

The compounds were also tested as fungicides in plate fungicide testsagainst Pythium spp., Rhizoctonia, Fusarium, I-lelminthosporium andStemphylliurn as shown in Table 2. The compounds were made up intoFormulation A and then added to agar culture of the fungi except for thetest with Stemphyllium which was a slide germination test. In the table,10 indicates 100% effectiveness and 0 indicates no effectiveness. Theconcentrations are expressed in p.p.m. (parts per million). TheStemphyllium results are qualitative only and hence instead of using thescale of 10 to 0 are recorded only as for inhibition and 0 for noinhibition.

Table 2 Pythinm Fusarium Rhizoctonia Helminth. Stemphyllium CompoundA3SCH=CCl2 10 10 4 0 8 2 4 0 A4SCH=OCI2 10 10 10 7 8 1 10 3 A1SOHOlCHGl8 3 2 O 5 2 0 0 0 0 AQSCHOlOHOlZ. 10 10 0 1O 10 0 10 7 0 10 4 O 0 OAsSCHClCHClz 10 1O 0 l0 7 0 10 8 0 10 7 0 0 0 111301120013 10 10 10 0 50 10 0 0 0 A2SOH2CC13- 10 10 10 1 6 l 5 2 A3SCH1CCls 10 0 2 0 2 0 4 0 00 A4SCH2C O13 10 10 10 5 10 7 10 10 0 1 1 Bactericide tests were run byincorporating the compounds in Formulation A and adding this mixture toan agar culture of the bacteria. The following positive bactericideactions were noted.

A SCCl=CHC1 against Erwinia carotovora at 1000 p.p.m.,

A SCCl CHCl against Pseudomonas coronafaciens at 1000 p.p.m. and againstXanthomonas vesicatoria at 1000 p.p.m.,

A SCH=CCl against each of Erwinia carotovora, Pseudomonas coronafaciensand Xanthomonas vesicazoria at 1000 p.p.m.,

A SCH=CCl against Erwinia carotovora at 1000 p.p.m. and 100 p.p.m.,against Pseudomonas coronafaciens at 1000 p.p.m. and 100 p.p.m., andagainst Xanthomonas vesicatoria at 1000 p.p.m.,

A SCH CCl against Erwinia carotovora at 1000 p.p.m.,

A SCH CCI against Pseudamonas coronafaciens at 1000 p.p.m.

What is claimed is:

1. A process of killing nematodes comprising subjecting the nematodes toa nematocidally effective amount of a compound having a formula selectedfrom the group consisting of 7 J12. z'i where Y is selected from thegroup consisting o --("J and where X is selected from the groupconsisting and with the proviso that when X is C H Y is o H C two of Z Zand Z are halogen of atomic weight 35 to 80 and the other member of Z Zand Z is hydrogen;

3 to 4 members of Z Z Z Z and Z are halogen of atomic weight 35 to 80and the remaining members of Z Z Z Z and Z; are hydrogen; and

R is selected from the group consisting of lower alkyl,

chloro, bromo and nitro.

2. A process of killing nematodes comprising subjecting them to anematocidally effective amount of N-(dichlorovinylthio) phthalimide.

3. A process of killing nematodes comprising subjecting them to anernatocidally effective amount of N-(dichlorovinylthio)cis-M-tetrahydrophthalimide.

4. A process of killing nematodes comprising subjecting them to anematocidally effective amount of N-(1,2,2- trichloroethylthio)phthalimide.

5. A process of killing nematodes comprising subjectwhere Y is selectedfrom the group consisting ss- -s where X is selected from the groupconsisting fl J I C and and with the proviso that when X is C H Y is twoof Z Z and Z are halogen of atomic weight 35 to and the other member ofZ Z and Z is hydrogen;

3 to 4 members of Z Z Z Z and Z are halogen of atomic Weight 35 to 80and the remaining members of Z Z Z Z and Z; are hydrogen; and

R is selected from the group consisting of lower alkyl,

chloro, bromo and nitro.

8. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of N-(trichloroethylthio) succinimide.

'9. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of N-(1,2,2-trichloroethylthio)succinimide.

10. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of N-(2,2,2- trichloroethylthio)succinimide.

11. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of N-(trichloroethylthio) phthalimide.

12. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of N-(l,2,2-

trichloroethylthio) phthalimide.

13. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of N-(trichloroethylthio)cis-M-tetrahydrophthalimide.

14. A process of killing fungi comprising subjecting said fungi to afungicidally effective amount of N-(1,2,2- trichloroethylthio cis-Atetrahydrophthalimide.

References Cited in the file of this patent UNITED STATES PATENTS2,553,770 Kittleson May 22, 1951 2,553,773 Cohen May 22, 1951 2,856,410Kittleson Oct. 14, 1958 3,036,088 Harris May 22, 1962

1. A PROCESS OF KILLING NEMATODES COMPRISING SUBJECTING THE NEMATODES TOA NEMATOCIDALLY EFFECTIVE AMOUNT OF A COMPOUND HAVING A FORMULA SELECTEDFROM THE GROUP CONSISTING OF